CN104483303B - The method that SERS method determines the red II of citrus in citrus - Google Patents
The method that SERS method determines the red II of citrus in citrus Download PDFInfo
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Abstract
The invention provides a kind of method that SERS method determines the red II of citrus in citrus, comprise the following steps：Citrus gross weight is beaten together and is fine into foam shape or pulpous state, it is purified using QuEChERS rapid extraction -ASEs, filter membrane obtains testing sample；250~600 μ L OTR202 reinforcing agents are sequentially added in sample injection bottle, 10~50 μ L samples prepare liquids and 50~150 μ LOTR103 reinforcing agents are mixed, this mixed volume need >=0.5mL；It is 50~200mW to set Raman spectrometer laser power, and resolution ratio is 2cm‑1, signal relative intensity scope is 0~60000, and the time of integration is 5~20s, integrates 1~3 time averagely, and filter smoothing parameter is 1；Under SERS system, Raman spectrum analysis is carried out to the red II of illegal additive citrus common in food, find out its corresponding Raman spectrum characteristic peak, using the qualitative features peak as the red II of illegal addition citrus in citrus, the method for setting up the red II of citrus in a kind of quick, easy, sensitive SERS detection citrus.
Description
Technical field
The present invention relates to food additives field, more particularly to a kind of application SERS method is determined in citrus
The red II of citrus method.
Background technology
The red II dyestuffs of citrus are also named the (abbreviation of solvent red 80:CR2), molecular formula is C18H16N2O3, chemical entitled 1- [(2,
5- Dimethoxyphenyls) azo]-beta naphthal, molecular weight is 308.331.The red II of citrus is Chinese red powder, water insoluble, molten
In aromatic hydrocarbon solvent.Reasonable employment will not constitute a threat to human body, by treated fruit in whole fruit (with dry weight
Meter) content no more than 2mg/L.The red II pigments of citrus after being dissolved through coordinative solvent, are only used for not processed morning
Ripe sweet orange pericarp is hyperchromic, and the real epidermis of consequences for use must not have volatile solvent residue.GB/T 2760-2011《Food additive
Plus agent uses sanitary standard》Clear stipulaties do not allow to add the red II pigments of citrus in food.Illegal retailer is in order to make profit, in violation of rules and regulations
Increase color and luster and the uniform coloring degree of sweet orange (mainly navel orange) fruit using this dyestuff as coloring agent, improve the market of fruit
Competitiveness.The ground fruit market such as Guangdong in 2004 and Hong Kong finds dyeing orange, red No. II of citrus being potentially carcinogenic containing disabling in succession
Pigment.
Currently for artificial synthesized colouring agent in food and the main still efficient liquid phase of the conventional detection method of azo dyes
Chromatography, high performance liquid chromatography GC-MS and AAS, although these cquipment for periodic inspection precision of method are high, stability
It is good, but testing cost is high, is difficult different occasion movements and uses and time-consuming, is unfavorable for carrying out large batch of sample detection sieve in real time
Look into, it is impossible to meet the live quick, demand of high-volume examination failed test sample.
Therefore, the problem of fast and effectively Food Safety Analysis method turns into the urgent need to address is set up.And surface increases
Haling graceful spectrum detection technique has sample treatment simple, and detection time is short, the informative that detection spectrum is reflected, is adapted to fast
Fast qualitative analysis, has some superiority in food inspection.
The content of the invention
The present invention is drawn the illegal red II of additive citrus common in food under SERS system
Graceful spectrum analysis, finds out its corresponding Raman spectrum characteristic peak, using the qualitative spy as the red II of illegal addition citrus in citrus
Peak, sets up a kind of quick, easy Raman spectrum method for detecting surface reinforcement.
Technical scheme comprises the following steps：
(1) citrus gross weight is beaten together and is fine into foam shape or pulpous state, it is purified using QuEChERS rapid extraction -ASEs,
Filter membrane obtains testing sample；
(2) 250~600 μ L OTR202 reinforcing agents, 10~50 μ L samples prepare liquids and 50 are sequentially added in sample injection bottle
~150 μ LOTR103 reinforcing agents are mixed, this mixed volume need >=0.5mL；
(3) application Raman spectrometer determines the sample in the sample injection bottle；Set Raman spectrometer laser power be 50~
200mW, resolution ratio is 2cm-1, signal relative intensity scope is 0~60000, and the time of integration is 5~20s, integrates 1~3 time and puts down
, filter smoothing parameter is 1；
If detecting to contain the red II of citrus in the red II of citrus Raman qualitative features peak, citrus；If there is not citrus
Red II Raman qualitative features peak, then do not contain the red II of citrus in citrus.
Wherein, the red II of citrus Raman qualitative features peak is 578 ± 3cm-1, 1282 ± 3cm-1, 1589 ± 3cm-1。
It is preferred that, in step (1), the step of QuEChERS rapid extraction -ASEs are purified to citrus slurries is：By citrus
Slurries add water to be well mixed with acetonitrile, is extracted with QuEChERS extraction agents box, acutely centrifuges standing after concussion, then take acetonitrile layer
In QuEChERS dispersive solid-phase extraction kits, shaking is centrifuged after mixing, and takes supernatant to cross film.
More there is choosing, claim 5.00g citrus slurries in centrifuge tube, add 5mL water, whirlpool is mixed, and adds 5.00mL second
Nitrile, whirlpool mix 1min, be added in QuEChERS extraction agent boxes shake after centrifuge stand, then take 2mL acetonitrile layers in
In QuEChERS dispersive solid-phase extraction kits, shaking 1min is centrifuged after mixing, the organic filter membrane for taking supernatant to cross 0.45 μm.
The red II of citrus is often made an addition in Juice or citrus fruit, is examined currently without specific national standard method
Survey.This research is purified using QuEChERS Rapid Extractions method II red to the prohibitive dye citrus of illegal additive in food, its
Processing method is simple, quick, and sample treatment is clean, and the rate of recovery is 89.1%~93.7%.Sensitivity is high, and surface increases in the method
Strong Raman spectrum II red to citrus detection is limited to 5mg/kg.Through liquid chromatography qualitative proving and comparisom, it can meet to field sample
The red II contents of citrus are more than 5mg/kg qualitative detection.
Brief description of the drawings
The invention will be further described below in conjunction with the accompanying drawings：
Fig. 1 is the red II of high performance liquid chromatography citrus standard curve；
Fig. 2 is the high-efficient liquid phase chromatogram of the red II of citrus and standard specimen in sample；
Fig. 3 is the red II of citrus SERS figure；
Fig. 4 is the red II Raman spectrograms of citrus in different samples.
Embodiment
Below in conjunction with the embodiment and accompanying drawing in the present invention, the technical scheme in the embodiment of the present invention is carried out it is clear,
It is fully described by, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
Embodiment 1：
1.1 instrument and equipment
High performance liquid chromatograph device:Agilent 1100, equipped with DAD detectors, Anjelen Sci. ＆ Tech. Inc of the U.S.；
Type Portable Raman spectrometer, Opto Trace Technologies Inc.；
Vortex mixer：XW-80A, Changzhou Nuo Ji Instrument Ltd..
1.2 reagents and sample
The red II standard substances of citrus：99%, it is purchased from Shanghai ANPEL Scientific Instrument Co., Ltd.；
Acetonitrile：Chromatographically pure, Merck KGaA company；
OTR202, Opto Trace Technologies Inc.；
OTR103, Opto Trace Technologies Inc.；
QuEChERS extraction agent boxes, including：
(1)6g MgSO4, Anjelen Sci. ＆ Tech. Inc of the U.S.；
(2) 1.5g sodium acetates, Anjelen Sci. ＆ Tech. Inc of the U.S.；
QuEChERS dispersive solid-phase extraction kits, including：
(1) 50mgPSA, Anjelen Sci. ＆ Tech. Inc of the U.S.；
(2)150mgMgSO4, Anjelen Sci. ＆ Tech. Inc of the U.S.；
Citrus：It is purchased from supermarket.
1.3 experimental method
1.3.1 the preparation of standard liquid
The red II standard items of 0.0100g citruses accurately are weighed in 100.00mL volumetric flasks, scale is settled to acetonitrile, are made
The 100.00 μ g/mL red II standard reserving solutions of citrus, are sealed in 4 DEG C of refrigerators and preserve, standby.
Accurate absorption 0.10,0.50,1.00,5.00, the red II standard reserving solutions of 10.00mL citruses are in 100mL capacity respectively
In bottle, scale is settled to acetonitrile, the red II standards work of citrus that 0.10,0.50,1.00,5.00,10.00 μ g/mL are made is molten
Liquid, for liquid chromatogram and the standard liquid to be measured of Raman spectrum analysis.
1.3.2 sample-pretreating method
Citrus gross weight is beaten together and is fine into foam shape or pulpous state, it is accurate to claim 5.00g in 15mL plastic centrifuge tubes, add 5mL
Water, whirlpool is mixed, and adds 5.00mL acetonitriles, and whirlpool mixes 1min, QuEChERS extraction agents box (including 6g MgSO4,
1.5g sodium acetates, it is therefore an objective to remove water), acutely after concussion, with 4000rm/min centrifugation 4min on centrifuge.Take again
2mL acetonitrile layers (purpose is to remove organic acid, sugar and lipid) in QuEChERS dispersive solid-phase extraction kits, shaking 1min is mixed
After even, with 4000rm/min centrifugation 4min on centrifuge, then take supernatant to cross film, with high performance liquid chromatograph and
Raman spectrometer is tested and analyzed.
1.3.3SERS sample detection methods
(1) standard specimen is detected：It is molten that 500 μ L OTR202 reinforcing agents, 20 μ L standards to be measured are sequentially added in 2mL glass sample injection bottles
Liquid, 100 μ L OTR103 Contrast agents, after whirlpool is well mixed, are put into sample cell measure.
(2) sample detection：Treated in 2mL glass sample injection bottles by sequentially adding 500 μ L OTR202 reinforcing agents, 20 μ L samples
Liquid, 100 μ L OTR103 Contrast agents are surveyed, after whirlpool is well mixed, sample cell measure are put into.
1.3.4HPLC with SERS instrument testing conditions
(1) HPLC testing conditions
Chromatographic column：ZORBAX C18150mm×4.6mm×5μm；Mobile phase：The aqueous formic acid of acetonitrile+1%=90+10
(Chen Yufang etc., 2011)；DAD detectors：Detection wavelength：510nm；Column temperature：30℃；Sample size：10.0μL；Flow velocity：1.0mL/
min。
(2) SERS testing conditions
Spectrometer laser power is 200mW；Resolution ratio is 2cm-1；Signal relative intensity scope is 0~60000；During integration
Between be 10s；Integrate 2 times averagely；Filter smoothing parameter is 1.
1.3.5HPLC the rate of recovery and Precision Experiment
The citrus sample containing the red II of 1.40mg/kg citruses of certain mass is weighed, and is separately added into 2.00mg/ wherein
The red II standard liquids of citrus of tri- various concentrations of kg, 4.00mg/kg and 6.00mg/kg, are determined with high performance liquid chromatography, respectively
6 parallel laboratory tests are carried out, the rate of recovery and precision for obtaining method are shown in Table 1.
1.3.6HPLC method detection limit
According to the detection limit of formula (1) computational methods.
LOD=3CVf/ (S/N) m (1)
In formula：C-it is sample introduction concentration (unit：μg/mL)；
V-it is constant volume (unit：mL)；
F-extension rate；
S/N-it is signal to noise ratio (can carry out automatically analyzing acquisition to collection of illustrative plates by work station)；
M-quality (unit：g).
1.3.7SERS detection limit
Take the red II Ramans standard liquid of the various concentrations citrus prepared in 1.3.1 to make an addition in citrus slurries, mix, with drawing
Graceful spectrum is detected that its minimum concentrations is the detection limit of this method.
2 results and analysis
The drafting of 2.1 standard curves and chromatogram
The red II standard liquids of the citrus of preparation are taken into 10 μ L respectively from low concentration to high concentration, surveyed with high performance liquid chromatography
It is fixed, peak area quantification qualitative according to retention time, using concentration as abscissa, peak area is ordinate, draws the red II of citrus mark
Directrix curve, is shown in Fig. 1.As can be seen from Figure 1：The red II of citrus standard working concentration has in the range of 0.10~10.00 μ g/mL
Good linear relationship, coefficient correlation is 0.9998.
Standard specimen chromatogram and sample drawing are shown in Fig. 2.In fig. 2, it is followed successively by from top to bottom：First figure is acetonitrile blank, the
Two figures are the sample chromatogram figure that the red II of citrus is illegally added containing 1.4mg/kg, and the 3rd figure is in the illegally red II of addition citrus
Blank sample in add the chromatograms of the red II standard liquids of 6.4mg/kg citruses, the 4th figure is that the red II of 5.0 μ g/mL citruses is marked
Quasi- solution chromatogram.As can be seen from the figure：The red II of citrus is in 3.0min or so appearances, and the pre-treatment of sample is preferable, no miscellaneous peak
Interference to object, the 3rd contrasts with second figure, after with the addition of the red II standard liquids of citrus (the 3rd figure), peak height
Apparently higher than sample (second figure), show to add the content after the red II standard specimens of citrus apparently higher than blank sample, it is actual with managing
By being consistent, it can determine whether out the red II pigments of citrus whether are illegally with the addition of in citrus by this, therefore, can be as Raman spectrum to mandarin orange
Exocarpium Citri Rubrum II qualitative detection sample.
2.2 rate of recovery and Precision Experiment
The red II of citrus recovery of standard addition and the result such as following table of precision.
The rate of recovery of table 4.1 and Precision Experiment (n=6) %
As can be seen from Table 1, under different spiked levels, the red II of citrus average recovery rate is 89.1%~93.7%, side
Method precision RSD is 5.58%~6.2%.This method rate of recovery is high, and precision is good, fully meets requirement of experiment.
The detection limit of 2.3HPLC methods
According to the detection limit of LOD=3CVf/ (S/N) m computational methods.
In formula：C=5.00, the solution concentration of sample introduction is 5.00 μ g/mL；V=5.00, constant volume is 5.00mL；F=
1.0, extension rate is 1.0 times；S/N=148, in C=5.00 μ g/mL, corresponding signal noise ratio is 148；M=
5.00, sample quality is called 5.00g.0.1mg/kg is limited to according to LOD=3CVf/ (S/N) m method detections for calculating HPLC.
The red II of 2.4 citruses SERS figure characteristic peak
From figure 3, it can be seen that the 578cm of gradient can be selected-1, 1282cm-1, 1589cm-1Characteristic peak be mandarin orange
Exocarpium Citri Rubrum II raman characteristic peak, as long as detecting these wave number deviations (± 3cm simultaneously in sample-1) characteristic peak, so that it may say
This bright sample contains the red II of citrus.The method can be whether to add the red II of citrus in citrus product qualitative judgement provide according to
According to.
The red II of 2.5 citruses and sample surfaces enhancing Raman spectrogram contrast
With reference to the red II of citrus characteristic peak, though sample substrate interference remains unchanged it can be seen that containing in sample than larger from Fig. 4
Some red II of citrus characteristic peak is obvious, can provide foundation whether to do qualitative judgement containing Basic Orange in citrus.
The red II of 2.6 citruses detection limit
With reference to red No. II minimum response concentration of citrus, show that the red II of SERS citruses SERS detections are limited to 5mg/kg.
3 brief summaries
(1) the red II of citrus is often made an addition in Juice or citrus fruit, is carried out currently without specific national standard method
Detection.This research is purified using QuEChERS Rapid Extractions method II red to the prohibitive dye citrus of illegal additive in food,
Its processing method is simple, quick, and sample treatment is clean.Through experiment draw the average recovery rate of this method for 89.1%~
93.7%, RSD are 3.6%~5.6%, and detection is limited to 0.1mg/kg, can be provided necessarily for the red II of citrus in citrus detection
Reference, meanwhile, provide strong foundation for the good qualitative detections of SERS II red to citrus.
(2) detection of the SERS to No. II red to citrus in citrus, its raman characteristic peak be 578 ±
3cm-1, 1282 ± 3cm-1, 1589 ± 3cm-1, detect quick, simple after sample extraction, and detection is limited to 5mg/kg.As long as sample
In contain these characteristic peaks simultaneously, the red II of citrus just can be quickly contained in judgement sample, the method can be used in citrus
Whether add citrus 2 and carry out qualitative detection, and will be played a significant role in quick detection.
(3) the illegal red II of additive citrus quick pretreatment method is searched out using QuEChERS technologies, with reference to Raman
Spectral technique establishes a set of pre-treating method simply, detects quick detection method.Through liquid chromatography qualitative proving and comparisom, energy
Meet the qualitative detection that II contents red to field sample citrus are more than 5mg/kg.
It can be that professional and technical personnel in the field realize or used that above-mentioned embodiment, which is intended to illustrate the present invention, to above-mentioned
Embodiment is modified and will be apparent for those skilled in the art, therefore the present invention includes but is not limited to
Above-mentioned embodiment, it is any to meet the claims or specification description, meet with principles disclosed herein and novelty,
The method of inventive features, technique, product, each fall within protection scope of the present invention.
Claims (3)
1. the method that SERS method determines the red II of citrus in citrus, it is characterised in that comprise the following steps：
(1) citrus gross weight is beaten together and is fine into foam shape or pulpous state, it is purified using QuEChERS rapid extraction -ASEs, by mandarin orange
Tangerine slurries add water to be well mixed with acetonitrile, is extracted with QuEChERS extraction agents box, acutely centrifuges standing after concussion, then take acetonitrile
Layer is in QuEChERS dispersive solid-phase extraction kits, and shaking is centrifuged after mixing, and takes supernatant to cross film, filter membrane obtains treating test sample
Product；
(2) 250~600 μ L OTR202 reinforcing agents, 10~50 μ L samples prepare liquids and 50~150 are sequentially added in sample injection bottle
μ L OTR103 reinforcing agents are mixed, this mixed volume need >=0.5mL；
(3) application Raman spectrometer determines the sample in the sample injection bottle；
If detecting to contain the red II of citrus in the red II of citrus Raman qualitative features peak, citrus；If there is not the red II of citrus
Raman qualitative features peak, then the red II of citrus is not contained in citrus；
The wherein described red II of citrus Raman qualitative features peak is 578 ± 3cm-1, 1282 ± 3cm-1With 1589 ± 3cm-1。
2. the method that SERS method according to claim 1 determines the red II of citrus in citrus, its feature exists
In title 5.00g citrus slurries add 5mL water in centrifuge tube, and whirlpool is mixed, and add 5.00mL acetonitriles, and whirlpool is mixed
1min, is added to after being shaken in QuEChERS extraction agent boxes and centrifuges standing, then take 2mL acetonitrile layers in QuEChERS dispersed solid phases
In extraction agent box, shaking 1min is centrifuged after mixing, the organic filter membrane for taking supernatant to cross 0.45 μm.
3. the method that SERS method according to claim 1 determines the red II of citrus in citrus, its feature exists
In in step (3), it is 50~200mW to set Raman spectrometer laser power, and resolution ratio is 2cm-1, signal relative intensity scope
For 0~60000, the time of integration is 5~20s, integrate 1~3 time it is average, filter smoothing parameter is 1.
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| CN107389654A (en) * | 2017-07-19 | 2017-11-24 | 合肥学院 | A kind of food additives detection method based on SERS |
| CN108362677A (en) * | 2018-01-22 | 2018-08-03 | 浙江大学 | A method of soil hydrolyzable nitrogen is quickly detected based on surface Raman enhancement technology |
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| CN103335995A (en) * | 2013-07-13 | 2013-10-02 | 福州大学 | Method for detecting synthetic pigments in food by utilizing raman enhanced spectrum |
| CN104101591A (en) * | 2014-07-24 | 2014-10-15 | 江西农业大学 | Fast detection method for surface enhanced Raman scattering of trace pesticide residues in oranges |
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| CN103335995A (en) * | 2013-07-13 | 2013-10-02 | 福州大学 | Method for detecting synthetic pigments in food by utilizing raman enhanced spectrum |
| CN104101591A (en) * | 2014-07-24 | 2014-10-15 | 江西农业大学 | Fast detection method for surface enhanced Raman scattering of trace pesticide residues in oranges |
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| Detection of thiabendazole applied on citrus fruits and bananas using surface enhanced Raman scattering;C. Müller et al.;《Food Chemistry》;20130907;第145卷;第814-820页 * |
| 脐橙果肉中噻菌灵农药的SERS快速检测研究;李俊杰等;《江西农业大学学报》;20141231;第36卷(第06期);第1229-1233页，尤其是第1231页第1-3、5段，第1232页第1段 * |
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